DE1543591C3 - - Google Patents
Info
- Publication number
- DE1543591C3 DE1543591C3 DE1543591A DE1543591A DE1543591C3 DE 1543591 C3 DE1543591 C3 DE 1543591C3 DE 1543591 A DE1543591 A DE 1543591A DE 1543591 A DE1543591 A DE 1543591A DE 1543591 C3 DE1543591 C3 DE 1543591C3
- Authority
- DE
- Germany
- Prior art keywords
- aldehyde
- methyl
- cyanthiophene
- thiosemicarbazone
- aldehydes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
- C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D495/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
in der R1 und R2 Wasserstoff bedeuten oder jeweils einer der Substituenten R1 und R2 Wasserstoff und der andere jeweils Methyl bedeutet.in which R 1 and R 2 are hydrogen or in each case one of the substituents R 1 and R 2 is hydrogen and the other is in each case methyl.
2. Verfahren zur Herstellung von Thiophen-2-aldehyd-thiosemicarbazonen der allgemeinen Formel2. Process for the preparation of thiophene-2-aldehyde thiosemicarbazones the general formula
CH=OCH = O
bedeutet, erhält, wenn man in an sich bekannter Weise Aldehyde der allgemeinen Formelmeans obtained when aldehydes of the general formula are used in a manner known per se
IOIO
1515th
2020th
CH=N-NH-C-NH2 CH = N-NH-C-NH 2
in der R1 und R2 Wasserstoffatome oder jeweils einer der Substituenten R1 und R2 Wasserstoff oder Methyl bedeutet, dadurch gekennzeichnet, daß man in an sich bekannter Weise Aldehyde der allgemeinen Formelin which R 1 and R 2 are hydrogen atoms or in each case one of the substituents R 1 and R 2 is hydrogen or methyl, characterized in that aldehydes of the general formula are used in a manner known per se
3535
in der R1 und R2 die angegebene Bedeutung haben, oder deren funktioneile Derivate mit Thiosemicarbazid umsetzt.in which R 1 and R 2 have the meaning given, or their functional derivatives are reacted with thiosemicarbazide.
4545
Es ist bekannt, daß Thiosemicarbazone von aromatischen und heterocyclischen Aldehyden in vivo eine Wirkung gegen das Vakzine-Virus (Pocken) besitzen. (D. Hamre et al, Proc. Soc. Exptl. Biol. Med. 73, 275 [1950], und R. L. Thompson et al, J. Immunol. 70, 229 [1953]).It is known that thiosemicarbazones of aromatic and heterocyclic aldehydes in vivo have an effect against the vaccine virus (smallpox). (D. Hamre et al, Proc. Soc. Exptl. Biol. Med. 73, 275 [1950], and R. L. Thompson et al, J. Immunol. 70, 229 [1953]).
Eine der in vivo bisher wirksamsten Verbindungen ist das N-Methyl-isatin-thiosemicarbazon (D. J. Bauer, Brit. J. Exptl. Pathol. 36, 105 [1955], Brit. J. Pharmacol. 15, 101 [I960]).One of the most effective compounds so far in vivo is N-methyl-isatin-thiosemicarbazone (D. J. Bauer, Brit. J. Exptl. Pathol. 36, 105 [1955], Brit. J. Pharmacol. 15, 101 [1960]).
Es wurde nun gefunden, daß man gegen das Vakzine-Virus hochwirksame Thiophen-2-aldehydthiosemicarbazone der allgemeinen FormelIt has now been found that thiophene-2-aldehyde-thiosemicarbazones which are highly effective against the vaccine virus the general formula
5555
N=CN = C
CH = OCH = O
CH=N-NH-C-NH,CH = N-NH-C-NH,
in der R1 und R2 Wasserstoffatome oder jeweils einer der Substituenten R1 und R2 Wasserstoff oder Methylin which R 1 and R 2 are hydrogen atoms or in each case one of the substituents R 1 and R 2 is hydrogen or methyl
6060
65 in der R1 und R2 die angegebene Bedeutung haben, oder deren funktioneile Derivate mit Thiosemicarbazid umsetzt. 65 in which R 1 and R 2 have the meaning given, or reacts their functional derivatives with thiosemicarbazide.
Als Ausgangsstoffe können beispielsweise herangezogen werden: 5-Cyanthiophen-2-aldehyd, 3- oder 4-Methyl-5-cyanthiophen-2-aldehyd bzw. deren funktionelle Derivate.The following can be used as starting materials, for example: 5-cyanthiophene-2-aldehyde, 3- or 4-methyl-5-cyanthiophene-2-aldehyde or their functional derivatives.
Die gegebenenfalls substituierten 5-Cyanthiophen-2-aldehyde können nach an sich bekannten Methoden aus 5-Halogenthiophen-2-aldehyden durch Einwirkung von Kupfer(I)-cyanid in einem polaren Lösungsmittel erhalten werden (J. org. Chem. 26, 2522, 2525 [1961]).The optionally substituted 5-cyanthiophene-2-aldehydes can be prepared from 5-halothiophen-2-aldehydes by action according to methods known per se obtained from copper (I) cyanide in a polar solvent (J. org. Chem. 26, 2522, 2525 [1961]).
Das Verfahren gemäß der Erfindung kann beispielsweise derart durchgeführt werden, daß man molare Mengen der Komponenten (1 Mol Aldehyd auf 1 Mol Thiosemicarbazid) aufeinander einwirken läßt. Es empfiehlt sich jedoch im allgemeinen die Mitverwendung eines Lösungs- oder Verteilungsmittels. Vorzugsweise arbeitet man in der 5- bis 20fachen Menge eines organischen Lösungsmittels, wobei insbesondere niedrigmolekulare Alkohole, beispielsweise Methanol, Äthanol, Propanol, Isopropanol und AIkoxyäthanole, wie Methoxy- und Äthoxyäthanol, in Betracht kommen. Eine Umsetzung der Komponenten in Wasser oder Gemischen der angegebenen Alkohole mit Wasser in allen Verhältnissen ist ebenfalls möglich.The method according to the invention can be carried out, for example, in such a way that molar amounts of the components (1 mole of aldehyde to 1 mole of thiosemicarbazide) interact leaves. In general, however, it is advisable to use a solvent or distributing agent. It is preferable to work in the 5 to 20 fold Amount of an organic solvent, in particular low molecular weight alcohols, for example Methanol, ethanol, propanol, isopropanol and alkoxyethanols, such as methoxy and ethoxyethanol, in Come into consideration. A reaction of the components in water or mixtures of the specified alcohols with water in all proportions is also possible.
Die Reaktionstemperatur kann zwischen Raumtemperatur und 1400C liegen, zweckmäßig arbeitet man bei 70 bis 900C.The reaction temperature can be between room temperature and 140 ° C., it is expedient to work at 70 to 90 ° C.
Die Reaktionszeiten betragen je nach Bedingungen und Temperaturen meist nur wenige Minuten.The reaction times are usually only a few minutes, depending on the conditions and temperatures.
Die Kondensation läßt sich ohne Katalysator durchführen; die Anwesenheit von katalytischen Mengen einer Säure ist aber für einen schnellen Reaktionsablauf von Vorteil. Als Säuren kommen beispielsweise niedrigmolekulare Fettsäuren, wie Essigsäure, in Frage.The condensation can be carried out without a catalyst; the presence of catalytic amounts an acid is advantageous for a rapid reaction process. The acids come, for example low molecular weight fatty acids such as acetic acid in question.
Im allgemeinen kristallisieren die Verfahrenserzeugnisse in reiner Form aus und lassen sich gegebenenfalls aus Lösungsmitteln Umkristallisieren.In general, the products of the process crystallize out in pure form and can optionally be removed Recrystallize from solvents.
Als Ausgangsstoffe können an Stelle der Aldehyde auch deren funktionell Aldehydderivate verwendet werden. Als solche kommen beispielsweise die Acetale, die Diacylverbindungen, Aldehydbisulfitverbindungen, Oxime oder Anile in Frage, die unter den oben beschriebenen Reaktionsbedingungen mit Thiosemicarbazid umgesetzt werden können.Functional aldehyde derivatives can also be used as starting materials instead of the aldehydes will. As such, for example, the acetals, the diacyl compounds, aldehyde bisulfite compounds, Oxime or anile in question, which under the reaction conditions described above with thiosemicarbazide can be implemented.
Die oben beschriebenen Umsetzungen der 5-Cyanthiophen-2-aldehyde bzw. deren funktioneller Derivate erfolgt nach üblichen Methoden, wie sie beispielsweise in Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Bd. 9, S. 913 bis 915, beschrieben sind.The reactions of 5-cyanthiophen-2-aldehydes described above or their functional derivatives are carried out by customary methods, such as, for example in Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Vol. 9, pp. 913 to 915, are described.
Die neuen Verfahrenserzeugnisse können als Heilmittel Verwendung finden. Insbesondere eignen sie sich für die Prophylaxe und Therapie der Variola (Pocken). Im Kaninchenversuch erweisen sich die Verfahrenserzeugnisse hinsichtlich der erzielten Wirkung (keine Pockenpustelausbildung) bei niederer Dosis und geringer Toxizität dem bekannten N-Me-The new process products can be used as medicinal products. In particular, they are suitable for the prophylaxis and therapy of variola (smallpox). In the rabbit experiment they prove to be Process products with regard to the effect achieved (no smallpox pustule formation) in the case of lower Dose and low toxicity to the well-known N-Me-
thyl-isatin-thiosemicarbazon sowie strukturverwandten Verbindungen als deutlich überlegen (s. Tabelle). Im Kaninchenversuch wurden folgende Verbindungen miteinander verglichen:thyl-isatin-thiosemicarbazon as well as structurally related ones Connections as clearly superior (see table). The following compounds were used in the rabbit experiment compared with each other:
I. S-Cyanthiophen^-aldehyd-I. S-Cyanthiophene ^ -aldehyde-
thiosemicarbazonthiosemicarbazone
Verfahrenserzeugnis,
11. Thiophen-2-aldehyd-thiosemicarbazonProcess product,
11. Thiophene-2-aldehyde-thiosemicarbazone
Strukturverwandte VerbindungStructurally related connection
(J. Immunol. 70, 229 (1953),(J. Immunol. 70, 229 (1953),
III. S-Bromthiophen^-aldehydthiosemicarbazon
Strukturverwandte Verbindung
(J. Immunol. 70, 222 (1953),
IV. 5-Nitrothiophen-2-aldehyd-III. S-bromothiophene ^ -aldehyde thiosemicarbazone
Structurally related connection
(J. Immunol. 70, 222 (1953),
IV. 5-nitrothiophene-2-aldehyde
thiosemicarbazon
Strukturverwandte Verbindung
(J. Immunol. 70, 222 (1953),
V. N-Methyl-isatin-thiosemicarbazon
als wirksam befundene, bekannte Verbindungthiosemicarbazone
Structurally related connection
(J. Immunol. 70, 222 (1953),
V. N-methyl-isatin-thiosemicarbazone
known compound found to be effective
(belgische Patentschrift 589 084 (1960).(Belgian patent 589 084 (1960).
VerabDuration of
Appointment
peroraldose
perorally
Infektionsdosis (Verdünnung)Finding
Infection dose (dilution)
in Tagenreaching
in days
Es wurden analog der Methode von G r ο t h (A. Herrlich, Handbuch der Schutzimpfungen, Springer-Verlag, Berlin/Heidelberg, 1965, S. 136) Kaninchen auf dem Rücken enthaart, wobei darauf zu achten ist, daß keine Hautverletzungen entstehen. Es wurden vom Vakzine-Virus Verdünnungen von 1: 1000, 1:10 000 und 1:100 000 hergestellt und jeweils 0,1 cm3 der Virus-Suspension mittels Intracutannadel als Quaddel injiziert. Ab 48 Stunden nach der Infektion können die ersten Reaktionen abgelesen werden. Die Beurteilung erfolgt nach folgendem Schema:Analogous to the method of G rο th (A. Herrlich, Handbuch der Schutzimpfungen, Springer-Verlag, Berlin / Heidelberg, 1965, p. 136) rabbits were depilated on their backs, care being taken that no skin injuries were caused. Dilutions of 1: 1000, 1:10 000 and 1: 100 000 were made of the vaccine virus and 0.1 cm 3 of the virus suspension was injected as a wheal using an intracutaneous needle. The first reactions can be read from 48 hours after infection. The assessment is carried out according to the following scheme:
— = keine Gewebsveränderungen, ± = leichte Rötung,- = no tissue changes, ± = slight reddening,
+ = Rötung mit Infiltration,
+ + = Pustelbildung, die in Nekrosen (N) übergeht, Haemorrhagien (H) entstehen läßt
oder zu einer Generalisation (G), d. h., Ausbreitung der Pockenpustel über den ganzen Körper und schließlich zum Tod
führen kann.+ = Reddening with infiltration,
+ + = Pustule formation that turns into necrosis (N), causes hemorrhages (H) or generalization (G), that is, the pox pustule spreads over the whole body and can ultimately lead to death.
Die Präparate wurden oral suspendiert in 0,3%iger Tylose je lmal an 5 aufeinander folgenden Tagen, beginnend am Tage der Infektion verabreicht.The preparations were orally suspended in 0.3% Tylose each once on 5 consecutive days, administered starting on the day of infection.
Darüber hinaus weisen die Verfahrenserzeugnisse eine sehr gute tuberkulostatische Wirkung in vivo auf.In addition, the products of the process have a very good tuberculostatic effect in vivo.
9,1 g (0,1 Mol) Thiosemicarbazid werden durch Erwärmen in 100 cm3 Wasser und 1,5 cm3 Eisessig gelöst und zu einer Lösung von 13,7 g (0,1 Mol) 5-Cyanthiophen-2-aldehyd in 100 cm3 Methanol gegeben. Das Reaktionsgemisch wird 15 Minuten unter Rückfluß erhitzt. Das Endprodukt kristallisiert meist schon in der Hitze aus, wird nach dem Erkalten9.1 g (0.1 mol) of thiosemicarbazide are dissolved by heating in 100 cm 3 of water and 1.5 cm 3 of glacial acetic acid and a solution of 13.7 g (0.1 mol) of 5-cyanthiophene-2-aldehyde in Given 100 cm 3 of methanol. The reaction mixture is refluxed for 15 minutes. The end product usually crystallizes out in the heat and becomes after cooling
abgesaugt, mit Wasser, kaltem Äthanol und Äther gewaschen und auf dem Dampfbad getrocknet.Aspirated, washed with water, cold ethanol and ether and dried on the steam bath.
Man erhält 19,1 g = 91% der Theorie 5-Cyanthiophen-2-aldehyd-thiosemicarbazon als gelbes kristallines Pulver vom Schmelzpunkt 2340C (Zers.).This gives 19.1 g = 91% of theory 5-cyanothiophene-2-aldehyde thiosemicarbazone as a yellow crystalline powder of melting point 234 0 C (dec.).
C7H6N4S2 (Molgewicht 210).
Berechnet ... N 26,7, S 30,5%;
gefunden .... N 26,8, S 30,5%.C 7 H 6 N 4 S 2 (molecular weight 210).
Calculated ... N 26.7, S 30.5%;
found .... N 26.8, S 30.5%.
Der als Ausgangsstoff verwendete 5-Cyanthiophen-2-aldehyd war durch Umsetzung von molaren Mengen 5-Bromthiophen-2-aldehyd mit Kupfer(I)-cyanid in Dimethylformamid durch 2stündiges Erhitzen unter Rückfluß, Abdestillieren des Lösungsmittels unter vermindertem Druck, Behandeln des Rückstands mit Wasser und Ausschütteln der Verbindung mit Essigester hergestellt worden. Man erhält 75% der Theorie 5-Cyanthiophen-2-aldehyd als gelbliche kristalline Masse vom Schmelzpunkt 92° C. Oftmals ist eine Reinigung durch Destillation von Vorteil. (Kp.12: 130 bis 135° C; F. 94° C).The 5-cyanthiophene-2-aldehyde used as starting material was obtained by reacting molar amounts of 5-bromothiophene-2-aldehyde with copper (I) cyanide in dimethylformamide by refluxing for 2 hours, distilling off the solvent under reduced pressure, treating the residue with Water and shaking out the compound with ethyl acetate. 75% of theory of 5-cyanthiophene-2-aldehyde is obtained as a yellowish crystalline mass with a melting point of 92 ° C. Purification by distillation is often advantageous. (Bp 12 : 130 to 135 ° C; mp 94 ° C).
9,1 g (0,1 Mol) Thiosemicarbazid werden durch Erwärmen in 100 cm3 Wasser gelöst und zu einer Lösung von 15,1 g(0,l Mol) S-Methyl-S-cyanthiophen-2-aldehyd in 100 cm3 Äthanol gegeben und 0,5 cm3 Eisessig zugesetzt. Das Endprodukt kristallisiert sofort aus, wird abgesaugt, mit 50% wäßrigem Alkohol und Äther gewaschen und auf dem Dampfbad getrocknet. 9.1 g (0.1 mol) of thiosemicarbazide are dissolved in 100 cm 3 of water by heating and to a solution of 15.1 g (0.1 mol) of S-methyl-S-cyanthiophene-2-aldehyde in 100 cm 3 Added ethanol and added 0.5 cm 3 of glacial acetic acid. The end product crystallizes out immediately, is filtered off with suction, washed with 50% aqueous alcohol and ether and dried on the steam bath.
Man erhält 19,7 g = 88% der Theorie 3-Methyl-5-cyanthiophen-2-aldehyd-thiosemicarbazon als gel-19.7 g = 88% of theory of 3-methyl-5-cyanthiophene-2-aldehyde thiosemicarbazone are obtained as gel
bes kristallines Pulver vom Schmelzpunkt 228° C (Zers.).besides crystalline powder with a melting point of 228 ° C (decomp.).
C8H8N4S2 (Molgewicht 224).
Berechnet ... N 25,0, S 28,6%; gefunden .... N 25,1, S 28,7%.C 8 H 8 N 4 S 2 (molecular weight 224).
Calculated ... N 25.0, S 28.6%; found .... N 25.1, S 28.7%.
Der als Ausgangsstoff verwendete 3-Methyl-5-cyanthiophen-2-aldehyd war durch Umsetzung von molaren Mengen 3-Methyl-5-bromthiophen-2-aldehyd (Kp.;,: 75 bis 800C) mit Kupfer(l)-cyanid in Dimethylformamid durch 2stündiges Erhitzen unter Rückfluß, Abdestiilieren des Lösungsmittels unter vermindertem Druck, Behandeln des Rückstands mit Wasser und Ausschütteln der Verbindung mit Essigester hergestellt worden. Man erhält nach Reinigung durch fraktionierte Destillation im Vakuum (Kp.! 5: 98 bis 102° C) 52% der Theorie S-Methyl-S-cyanthiophen-2-aldehyd als gelblich kristalline Masse vom F. 86 bis 88° C.The 3-methyl-5-cyanthiophen-2-aldehyde used as starting material was obtained by reacting molar amounts of 3-methyl-5-bromothiophene-2-aldehyde (bp.;,: 75 to 80 0 C) with copper (l) - cyanide in dimethylformamide by refluxing for 2 hours, distilling off the solvent under reduced pressure, treating the residue with water and shaking the compound with ethyl acetate. After purification by fractional distillation in vacuo (bp 5 : 98 to 102 ° C.), 52% of theory S-methyl-S-cyanthiophene-2-aldehyde is obtained as a yellowish crystalline mass with a melting point of 86 to 88 ° C.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19511543591 DE1543591A1 (en) | 1951-01-28 | 1951-01-28 | Process for the preparation of thiophene-2-aldehyde thiosemicarbazones |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19511543591 DE1543591A1 (en) | 1951-01-28 | 1951-01-28 | Process for the preparation of thiophene-2-aldehyde thiosemicarbazones |
| DEF0049285 | 1966-05-25 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DE1543591A1 DE1543591A1 (en) | 1971-11-25 |
| DE1543591B2 DE1543591B2 (en) | 1974-05-16 |
| DE1543591C3 true DE1543591C3 (en) | 1974-12-12 |
Family
ID=25752845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19511543591 Granted DE1543591A1 (en) | 1951-01-28 | 1951-01-28 | Process for the preparation of thiophene-2-aldehyde thiosemicarbazones |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1543591A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0219451B1 (en) * | 1985-08-20 | 1991-03-20 | Sandoz Ag | Semicarbazones and thiosemicarbazones |
| US7521062B2 (en) * | 2002-12-27 | 2009-04-21 | Novartis Vaccines & Diagnostics, Inc. | Thiosemicarbazones as anti-virals and immunopotentiators |
-
1951
- 1951-01-28 DE DE19511543591 patent/DE1543591A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| DE1543591A1 (en) | 1971-11-25 |
| DE1543591B2 (en) | 1974-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE2238504C3 (en) | l-Phenoxy-S-alkylaminopropan ^ -ol derivatives | |
| DE1543591C3 (en) | ||
| DE2427272C3 (en) | 1- (2- (β-Naphthyloxy) ethyl) -3-methyl-pyrazolone- (5), method and use as an antithrombotic | |
| DE1568526A1 (en) | Process for the preparation of bis-thiosemicarbazones | |
| DE2432392C3 (en) | Tris (2-hydroxyethyl) ammonium orthocresoxyacetate, process for its production and pharmaceuticals based on it | |
| DE2457309A1 (en) | 2-PHENYLHYDRAZINOTHIAZOLINE AND 2-PHENYLHYDRAZINOTHIAZINE DERIVATIVES AND THEIR USE AND METHOD FOR MANUFACTURING THE SAME | |
| DE2923817C2 (en) | (3-Alkylamino-2-hydroxyproposy) -furan-2-carboxylic acid anilides and their physiologically acceptable acid addition salts and processes for their preparation, as well as pharmaceuticals containing these compounds | |
| DE2439284C2 (en) | 2-Phenyl-3-amino-4-acetyl-5-methylpyrrole, its salts and pharmaceutical preparation containing these compounds | |
| DE1302662B (en) | ||
| DE1695790C3 (en) | S-phenoxythionocarbonyl derivatives of vitamin B deep 1 | |
| DE1795384C3 (en) | 1 H-2,3-Benzoxazines, processes for their production and pharmaceuticals | |
| DE2942065A1 (en) | NEW 1,6-NAPHTHYRIDINE DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND AGENT AGAINST Dizziness, AND FOR IMPROVING THE CEREBRAL CIRCULATION THAT CONTAINS THESE DERIVATIVES | |
| DE2239606A1 (en) | 4-PHENOXY 3-HYDROXY BUTYRAMIDINE AND DERIVATIVES | |
| DE2544702C3 (en) | Nitroimidazolyl vinyl thiadiazoles | |
| AT219020B (en) | Process for the preparation of new N-substituted amino-norcamphanderivaten and their acid addition salts and quaternary ammonium compounds | |
| DE1445505C3 (en) | 2-Phenylamino-13-diazacyclopentene- (2) substituted in the phenyl nucleus | |
| DE2312256C3 (en) | 5-pyrazole acetic acid derivatives, processes for their preparation and pharmaceutical compositions containing them | |
| DE1545730C (en) | Process for the production of substituted azines | |
| DE1620436C (en) | Carboxamidoalkyl 1,3 benzoxazin 2 one derivatives and processes for their preparation | |
| AT225188B (en) | Process for the preparation of new, 3-substituted derivatives of 1- (5-nitrofurfurylidene-amino) -hydantoin | |
| DE2133082C3 (en) | Q-Methyl-S-benzoyl-e-methoxyindolyl-l) -acetic acid glyceryl ester, i Process for their preparation and pharmaceuticals | |
| AT295526B (en) | Process for the preparation of new 1,2,5-thiadiazole derivatives and their salts | |
| AT236407B (en) | Process for the preparation of new benzenesulfonyl-alkylene-semicarbazides | |
| AT234109B (en) | Process for the preparation of new benzenesulfonylsemicarbazides | |
| AT236941B (en) | Process for the preparation of new substituted benzimidazoles and their acid addition salts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C3 | Grant after two publication steps (3rd publication) | ||
| E77 | Valid patent as to the heymanns-index 1977 | ||
| EHJ | Ceased/non-payment of the annual fee |